格林納試劑輔助合成鋁金屬錯合物及其內酯之開環聚合研究

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姓名

許又仁(HSU,YU-JEN) 查詢紙本館藏

畢業系所

化學學系

論文名稱

格林納試劑輔助合成鋁金屬錯合物及其內酯之開環聚合研究

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摘要(中)

傳統塑膠產品導致的污染已成為全球的嚴重問題，而利用各種內酯去進行開環聚合反應得到的聚酯具有生物可降解性和生物相容性，可以取代石化產業量產的不可降解塑膠，而達到環保永續的願景。本實驗利用格林納試劑輔助合成出一系列鋁錯合物。再將各種鋁金屬錯合物去測試內酯之開環聚合反應。例如: ε-己內酯和左旋丙交酯這類常見單體。並且利用測試不同催化劑/單體/起始劑的比例去優選出高產率並且分子量分佈度較窄的條件。測試其開環聚合的動力學反應，並發現開環反應之動力學對單體和催化劑皆為一級反應。在常溫下利用鋁錯合物對ε-己內酯進行開環聚合能以高產率 (ε-CL conv.= 98% in 3 min)得到分子量分佈度較窄的分子量分散性 (Ð = 1.065)，且得到最佳的kobs為1.023 min-1。並且其他用系列的鋁錯合物對ε-己內酯進行開環聚合都能以高產率得到窄分佈度的分子量分散性。

摘要(英)

The pollution caused by traditional plastic products has become a serious global issue. However, utilizing various lactones for ring-opening polymerization to produce polyesters with biodegradability and biocompatibility offers a promising solution to replace non-degradable plastics produced by the petrochemical industry, thereby achieving the vision of environmental sustainability. In this experiment, Grignard reagents were employed to help the syntheses of aluminum complexes. Subsequently, various aluminum metal complexes were tested for their catalytic activity in the ring-opening polymerization of lactones such as ε-caprolactone and L-lactide. Different ratios of catalyst/monomer/initiator were tested to optimize conditions for high yield and narrow molecular weight distribution. The kinetics of the ring-opening polymerization reaction were examined, revealing that the kinetics of the ring-opening reaction were first-order with respect to both the monomer and the catalyst. At room temperature, the best result for ε-caprolactone achieved 98% conversion in 3 min) and narrow molecular weight distribution (Ð = 1.065), with the optimal kobs being 1.023 min^-1. Similarly, the other Al complexes all yielded narrow molecular weight distributions at high yields when reacted with ε-caprolactone.

關鍵字(中)

★ 開環聚合反應
★ 格林納試劑反應
★ 鋁錯合物

關鍵字(英)

★ ring-opening polymerization
★ Grignard reagents
★ Al complexes

論文目次

目錄

國立中央大學圖書館學位論文授權書 ........................................................................... ii
中文摘要 .......................................................................................................................... iii
Abstract ............................................................................................................................ iv
謝誌 ................................................................................................................................... v
目錄 .................................................................................................................................. vi
圖目錄 .............................................................................................................................. ix
表目錄 ............................................................................................................................... x
第一章緒論 ........................................................................................................... 1
1-1 前言 ........................................................................................................... 1
1-2 開環聚合反應 ........................................................................................... 3
1-3 環酯類化合物 ........................................................................................... 4
1-3-1 環內酯單體- ε-己內酯 .............................................................................. 5
1-4 鋁金屬催化劑 ........................................................................................... 6
1-4-1 催化劑參考 ............................................................................................. 10
1-4-2 三苯基鋁催化劑參考 ............................................................................. 16
1-4-3 三苯基鋁催化劑 ..................................................................................... 22
1-5 錯合物滴定 ............................................................................................. 25
1-6 研究動機 ................................................................................................. 28
第二章實驗部分 ................................................................................................. 29
2-1 實驗藥品 ................................................................................................. 29
vii

2-2 鑑定儀器 ................................................................................................. 31
2-3 鋁金屬錯合物的合成 ............................................................................. 32
2-3-1 三苯基鋁的合成 ..................................................................................... 32
2-3-2 三萘基鋁的合成 ..................................................................................... 33
2-3-3 三對苯甲基鋁的合成 ............................................................................. 34
2-3-4 三對苯甲氧基鋁的合成 ......................................................................... 35
2-4 鋁金屬錯合物應用於單體開環聚合 ..................................................... 37
2-5 GPC樣品處理步驟 ................................................................................. 38
第三章結果與討論 ............................................................................................. 39
3-1 三苯基鋁的開環聚合反應 ..................................................................... 39
3-1-1 三苯基鋁對內酯進行開環聚合反應 ..................................................... 40
3-1-2 三苯基鋁對ε-己內酯進行開環聚合反應的優選 ............................... 42
3-1-3 三苯基鋁對ε-己內酯進行的開環聚合動力學反應 ........................... 44
3-2 三萘基鋁的開環聚合反應 ..................................................................... 47
3-2-1 三萘基鋁對ε-己內酯進行開環聚合反應 ............................................. 48
3-2-2 三萘基鋁對ε-己內酯進行的開環聚合動力學反應 ........................... 50
3-3 三對苯甲基鋁的開環聚合反應 ............................................................. 53
3-3-1 三對苯甲基鋁對ε-己內酯進行開環聚合反應 ................................... 54
3-3-2 三對苯甲基鋁對ε-己內酯進行的開環聚合動力學反應 ................... 56
3-4 三對苯甲氧基鋁的開環聚合反應 ......................................................... 62
3-4-1 三對苯甲氧基鋁對ε-己內酯進行開環聚合反應 ............................... 63
3-4-2 三對苯甲氧基鋁對ε-己內酯進行的開環聚合動力學反應 ............... 65
viii

3-5 四種催化劑的開環聚合動力學反應比較 ............................................. 71
第四章結論 ......................................................................................................... 74
參考文獻 ......................................................................................................................... 75
附錄 ................................................................................................................................. 77
NMR圖譜 .................................................................................................................... 77
滴定數據 ................................................................................................................... 107
GPC數據 ................................................................................................................... 127
Turnitin比對結果 ......................................................................................................... 136

參考文獻

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指導教授

吳國暉(Kuo-Hui Wu)

審核日期

2024-8-20

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